Encapsulated activator and its use to trigger a gelling system by physical means

ABSTRACT

The present disclosure relates to aqueous gelling systems comprising an encapsulated polymerization accelerator with water soluble or dispersable monomers comprising acrylated or methacrylated polyethylene and/or polyoxypropylene monomers and a polymerization initiator dispersed in said monomers, useful i.a. for sealing subterranean environments or consolidation of a soil or sealing of a subterranean structure.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.14/004,304 filed Nov. 14, 2013 which is a U.S. national stage entryunder 35 U.S.C. § 371 of International Application No. PCT/EP2012/053970filed Mar. 8, 2012, which claims priority to EP Application No.11157866.2 filed on Mar. 11, 2011 the whole content of this applicationbeing herein incorporated by reference for all purposes.

The current invention relates to a polyurethane encapsulated acceleratorof an (meth)acrylate gelling system to be triggered by physical meanssuch as high shear, high pressure, temperature, crushing shearing or anycombination of the above, and a process for the preparation of thatsystem.

Stopping a fluid leak located in a non-accessible spot like a buriedpipe, walls of a tunnel or tank, is one of the main technical problemsthat operators may encounter. In severe cases, the amount of fluid lostcan be very important. There is then a high risk that the leak cannot befixed with hazardous events which might be occurred if the leaking fluidis inflammable, explosive, harmful to the environment or toxic.

In general, to solve this problem, operators decide to inject any typeof plugging system such as particles, fibres or cement hoping that theleaks will be filled or obtruded and that they can restore the fluidproof in the pipe or tank. Another approach consists in developing“smart” systems which may set in a controlled way and could be injectedto the leaking spot itself. There, a lot of time would be saved betweeninitiation of the leak or spill, and repairing then resuming the flow orthe storage of the fluid.

Those plugging systems can be employed especially but not exclusively,for sealing subterranean environments and for consolidation of soils andsealing of subterranean structures, such as underground railway tunnels,sewers, underground car parks, storage ponds, swimming pools, mineshafts and dams. Among the many technical solutions which have beenproposed, cement grouts, silicate grouts and synthetic resin grouts canbe mentioned. Synthetic resins derived from unsaturated aliphatic acids,more specifically from acrylic acid and methacrylic acid, have been alsoespecially recommended.

Thus, Patent FR-A-1,113,937 describes the use of an acrylic acidderivative, such as acrylamide, Nalkylacrylamides, acrylonitrile alkylacrylates and metal acrylates, and of an alkylidenediacrylamide.

A critical disadvantage of such compositions lies in the potentialtoxicity of some of these compounds, more particularly in the case ofacrylamide based compositions.

The ecological demands of non toxicity of the products which may be incontact with water have led to the investigation of substitutecompounds.

Thus, Patent GB-A-1,303,456 describes compositions containing ahydroxyalkyl acrylate or methacrylate which may be coupled with analkylene glycol diacrylate or dimethacrylate, a soluble silver salt anda metal persulphate. These compositions cannot contain highconcentrations of monomers because the exothermicity caused by theirpolymerisation results in a high expansion and in the formation offoams, and this interferes with some applications, especially in thecase of operations for plugging cracks in subterranean structures. Themajor disadvantage of such composition is the control of the settingtime. Indeed, in many applications leaking zones are not accessible andoften far from the pumping/injection equipment. As a consequencedelaying agents have been evaluated to enable the use in remotelocations and even at elevated temperature as mentioned for example inGB 2226066(A)

Generally speaking no system has given fully satisfying results in termsof control accuracy and there is still a strong demand for an improvedgelling system.

The instant invention relates to such an improved system and, moreprecisely to a process for the preparation of an encapsulatedaccelerator to trigger a quick gelation of a polymerizable system.

More precisely the invention relates to a process for the encapsulationof a polymerization accelerator of water soluble or water dispersablemonomers (typically water soluble or dispersable monomers comprisingacrylated or methacrylated polyoxyethylene and/or polyoxypropylenemonomer), said process comprising the steps of

-   -   a) providing an reverse emulsion containing, in an oil phase, a        water solution or dispersion (referred as W1) containing said        polymerisation activator, the oil phase being (or at least        including) a heat curable mixture of an isocyanate and a        polyalkyldiene hydroxylated or polyol,    -   b) pouring the reverse emulsion of step a) in a water phase        (referred as W2) to make a multiple emulsion water/oil/water,        containing drops of activators as the internal water phase and,        then,    -   c) heating the multiple emulsion obtained in step b) at a        temperature of between 50 and 95° C., in order to cure the        polyisocyanate in polyurethane and obtain drops of activator        (W1) enclosed in shells of polyurethane dispersed in water (W2).

The current invention also relates to a specific gelling system based onthe encapsulated accelerator as obtained according to steps a) to c) andfurther comprising water soluble or water dispersable acrylated ormethacrylated polyoxyethylene and/or polyoxypropylene monomers togetherwith polymerization initiators such as peroxides.

This gelling system comprises:

-   -   i) water soluble or dispersable monomers comprising acrylated or        methacrylated polyoxyethylene and/or polyoxypropylene monomers    -   ii) a polymerization initiator dispersed in said monomers i),        and    -   iii) a encapsulated polymerization accelerator as obtained in        the process of the invention.

According to a specific embodiment the polymerization initiators ii) maybe encapsulated with the accelerator iii). In that case, the initiatorsand the accelerator are generally both in the internal water phaseinside the capsules obtained according to the process of the invention.Such a co-encapsulation may be obtained e.g. by providing in step a) ofthe process of the invention an emulsion which comprise both theinitiators and the accelerator in the water solution or dispersion (W1).

Whatever the exact nature of the gelling system, the gelling operationis carried out through a polymerization reaction initiated by release ofthe previously encapsulated accelerator in the water soluble ordispersable resin. In order to achieve that release at the appropriatetiming for the application, the accelerator is encapsulated before use,by the multiple emulsion process of the current invention. This releaseis obtained by any physical means allowing a release of thepolymerization accelerator from their polyurethane capsules, for exampleby high shear; high pressure; temperature crushing; and/or shearing.

Optionally, in step a), a solvent or plasticizer can be added to the oilphase. This solvent or plasticizer may for example be di-isobutyl esterof succinate glutarate or adipate. The addition of solvent orplasticizer allows to tune the mechanical properties of the polyurethaneshells.

Optionally in step a), a non-ionic surfactant is added to the waterphase W1, wherein said activator is dispersed or in solution. Thenon-ionic surfactant can be for example a di-C₁-C₈ alkyl ester of asaturated or unsaturated fatty acid having 12 to 22 carbon atoms.

Preferably, the water phase W2 of step b) contains a mineral salt, forexample NaCl and xanthan gum or another similar polymer. The mineralsalt is used in order to balance the osmotic pressure to prevent thereverse emulsion of step a) from bursting. Xanthan gum is used asprotective colloid and rheological agent. Any other similar polymer maybe used, including, e.g., gelatin, pectin derivative of cellulose,Arabic gum, guar gum, locust bean gum, tara gum, cassia gum, agar,modified starch such as n-octenyl starch or porous starch alginates,carraghenanes, chitosan, scleroglucan, diutan polyvinyl alcoholpolyvinyl pyrrolidone and mixtures thereof.

The polymerization accelerator which is used in the process and in thegelling system of the instant invention is advantageously a compoundwhich accelerates the polymerization of water soluble or waterdispersable monomers comprising acrylated or methacrylatedpolyoxyethylene and/or polyoxypropylene monomer (also called“macromonomers” due to the presence of polyoxyethylene and/orpolyoxypropylene chain in the monomer).

The polymerization accelerator which is used in the process of watersoluble or water dispersable macromonomers having the following generalformula (I):CH₂═CR¹—CO—(O—CH₂—CHR²)_(n)—OR³  (I)

wherein:

-   -   R¹ is a hydrogen atom or a methyl radical,    -   R² is a hydrogen atom or a methyl radical and    -   R³ is a hydrogen atom, a methyl radical or a CH₂═CR¹—CO— group    -   n is a whole or fractional number from 3 to 25.

The gelling system of the invention preferably include such watersoluble or dispersable macromonomers of formula (I).

Preferred water soluble or water dispersable monomers include a mixtureof methacrylate modified polyethylene oxide. Polyethyleneoxide chain ishere about 1000 g/mol as short chains are not hydrophilic enough balancethe hydrophobicity of the methacrylate end groups (especially at hightemperature and high salinity) on the other hand, longer chains lead toless reactive molecules Advantageous monomers are of the formulae

wherein n is a number between 15 and 25, limits included, and/or

wherein n is a number between 10 and 20, limits included.

In addition, these monomers are non-volatile, classified as polymers andshow no toxicity.

According to a specific embodiment, the water soluble or waterdispersable monomers used in the composition of the invention is amixture comprising at least two distinct kinds of monomers of formula(I), namely a first part of monomers wherein R³ is a methyl radical(herein referred to as monofunctional monomers I-1); and a second partof monomers wherein R³ is a CH₂═CR¹—CO— group (herein referred to asbisfunctional monomers I-2). According to an economical process, thismixture of monomers may advantageously be prepared by reacting a mixtureof two compounds (A1) and (A2) Having the following formulae:HO—(O—CH₂—CHR²)_(n)—OMe  (A1)HO—(O—CH₂—CHR²)_(n)—OH  (A2)

wherein R² is as defined above,

with a (meth)acrylic acid, chloride or anhydride (preferably ananhydride), typically a (meth)acrylic anhydride of formula (CH₂═CR¹—C)₂Owherein R¹ is as defined above.

Advantageously, in this preparation process, compounds (A1) and (A2) areused so as to obtain a mean number of OH group of between 1.1 and 1.5(A1 bears one OH and (A2) bears two). In this connection, it istypically preferred for the molar ratio (A2)/(A1) to be of between 10:90to 50:50.

Depending on the end use temperature conditions, either water solublepersalts like sodium persulphate or ammonium persulphate for lowtemperature (10 to 40° C. or water soluble or water dispersibleperoxides like tertiobutyl hydroperoxide (TBHP) tertio amylhydroperoxide and cumene hydroperoxide for temperature above 40° C. areused as polymerization initiators and mixed with the monomers withoutany reaction within at least 2 to 3 hours at the target temperature. Thepolymerization reaction of the monomers can easily be triggered by theaddition to said monomers of an amine accelerator. A stiff gels setsthen within a few minutes to a few hours depending on targetedapplication and on how far from the injection point versus pumping rate.The gel plug is to be placed, with the combined action of the initiatorand accelerator whose concentrations are adapted to the conditions(essentially the temperature) of the monomers in the gelling remotelocation.

The mixture of:

-   -   i) water soluble or dispersable monomers comprising an acrylate        or methacrylate polyoxyethylene and/or polyoxypropylene monomer,        and    -   ii) polymerization initiators dispersed in i)

is stable in the storage or injection conditions but starts topolymerize upon addition and contact with the accelerator in thepressure and temperature conditions of the remote location to betreated.

The polymerisation accelerator, also called an activator, is generallyan amino compound like an alkylamine, polyalkylen amine or poly alkylenimine preferably comprising tertiary amino groups and whose alkyl oralkylen part comprises 2-4 carbon atoms.

Primary or secondary amines or amine hydrochlorides can also be employedbut the polymerisation rate obtained with these accelerators is lowerthan with tertiary amines.

The amine polymerisation accelerator may include other chemicalfunctional groups in its formula such as, for example nitrile orhydroxyl or ester functional groups.

The ester functional groups may, in particular, originate from theesterification with acrylic acid or methacrylic acid of one or morehydroxyl functional groups present in the formula of the amine.

Among the preferred tertiary amines there may be mentioneddiethylaminopropionitrile, triethanolamine, dimethylaminoacetonitrile,diethylenetriamine, N,N-dimethylaniline, dimethylaminoethyl methacrylatedimethylaminoethyl acrylate, triethanolamine methacrylate andtriethanolamine acrylate.

A preferred accelerator is a polyethyleneimine (PEI) commerciallyavailable from BASF under the name of Lupasol®.

The accelerator is usually used at levels from 0.01% to 10% by weightover the weight of the polymerizable monomers, and preferably from 0.1%to 1.0%. Other accelerators, catalysts or co-accelerators can be usedlike metal ions such as copper or iron as catalysts of the activation.

The isocyanates for which the invention is most advantageous are alphaomega-aliphatic diisocyanates.

These aliphatic diisocyanates, to be condensed with polyamines/polyols,are either isocyanate molecules, referred to as monomers, that is to saynon poly-condensed, or heavier molecules resulting from one or moreoligocondensation(s), or mixtures of the oligocondensates, optionallywith monomer.

As will be clarified subsequently, the commonest oligocondensates arebiuret, the dimer and the trimer (in the field under consideration, theterm “trimer” is used to describe the mixtures resulting from theformation of isocyanuric rings from three isocyanate functional groups,in fact, there are, in addition to the trimer, heavier products areproduced during the trimerization reaction). Mention may in particularbe made, as monomer, of polymethylene diisocyanates, for example, TMDI(TetraMethylene Diisocyanate) and HDI (Hexamethylene Diisocyanate of theformula OCN—(CH₂)₆—NCO and its isomers (methylpentamethylenediisocyanate)]

It is desirable, in the structure of the or of one of the isocyanatemonomer(s), for the part of the backbone connecting two isocyanatefunctional groups to comprise at least one polymethylene sequence.Mention may also be made of the compounds resulting from thecondensation with diols and triols (carbamates and allophanates) undersubstoichiometric conditions. Thus, in the isocyanate compositions, itis possible to find isocyanurate functional groups, which can beobtained by catalyzed cyclocondensation of isocyanate functional groupswith themselves, urea functional groups, which can be obtained byreaction of isocyanate functional groups with water or primary orsecondary amines, biuret functional groups, which can be obtained bycondensation of isocyanate functional groups with themselves in thepresence of water and of a catalyst or by reaction of isocyanatefunctional groups with primary or secondary amines, urethane functionalgroups, which can be obtained by reaction of isocyanate functionalgroups with hydroxyl functional groups.

The shells of polyurethane obtained in step c) have typically an averagediameter of between 10 and 1500 μm, preferably between 300 and 800 μm.

The instant invention furthermore relates to a process for sealingsubterranean environments and consolidation of soils and sealing ofsubterranean structures comprising underground railway tunnels, sewers,underground car parks storage ponds, swimming pools, mine shafts anddams.

This process comprises the steps of:

-   -   e1) injecting into said environments soil or structure an        aqueous gelling system as defined above, comprising a        polymerization accelerator encapsulated in polyurethane capsules        and monomers, and    -   e2) triggering the polymerisation of the resin by physical        means, for example high shear, high pressure, temperature,        crushing, and/or shearing, whereby the encapsulated        polymerization accelerator is released from the polyurethane        capsules.

The invention will now be further illustrated by the followingillustrative examples.

EXAMPLE 1

A specific gelling system was prepared by following the following steps:

Step a):

the aqueous solution of Polyethyleneimine (PEI, Lupasol P from BASF) isdispersed in mixture of OH functionalized butadiene (Poly BD R45HT-LOfrom Sartomer), isophorone di-isocyanate trimer supplied diluted with30% wt butyl acetate (Tolonate IDT 70B from Perstorp) and diluted withRhodiasolv DIB (succinate, glutarate, adipate diisobutyl ester fromRhodia).

In order to ease the emulsification process, the emulsion of PEI in OHfunctional butadiene diluted with DIB is first made, and, then, theisocyanate is added to the already formed emulsion.

The particle size of the emulsion is set by acting on the agitationspeed.

The different quantities of ingredients are gathered in the followingtable 1:

TABLE 1 Ingredients Weight (g) OH functionalized butadiene Poly BDR45HT-LO 186.9 from Sartomer DIB 186.9 PEI 532.7 Tolonate IDT 70B fromperstorp 93.5 Total 1000.0

The mixing time after the addition of isocyanate is set to 5 mn. As aconsequence, the reverse emulsion is quickly transferred to the aqueousphase to form the multiple emulsion of step b)

Step b)

The reverse emulsion from step a) is then dispersed under vigorousstirring conditions to achieve the multiple emulsion. A very good andhomogeneous mixing efficiency is needed at that stage to maintain aparticle size distribution as narrow as possible.

To stabilize the suspension and avoid bursting of the capsules while thepolyurethane is not fully crosslinked the dispersion is made in a saltedxanthan solution. The salt (here NaCl at 20% wt) ensure the osmoticpressure balance between the inner PEI and outer xanthan solutionphases. A mismatch of osmotic pressure would cause a burst of theinverse emulsion. Xanthan is used here as a “protective colloid” andrheological agent. Indeed, it shows very good suspensive properties aswell as stabilization of the emulsion in salt water and even at elevatedcure temperature (up to 80° C. here).

As long as an homogeneous mixing is ensured during step b), the particlesize distribution is directly linked to the mixing speed. Here arotation speed of 280 RPM gives a particle size of approx 400 μm.

Typical operating conditions are reported here below:

-   -   transfer of emulsion of step a) to the reactor (containing the        0.45% wt xanthan in 20% wt NaCl water solution) under shear 280        RPM heated to 66° C. (envelope temperature)    -   after addition maintain agitation at 280 RPM for 15 mn    -   reduce speed to minimal 37 RPM and maintain for 2 hrs for curing        of the elastomer

For 1000 g emulsion from step 1 quantities necessary for the second stepare reported in table 2 below:

ingredients weight(g) deionized water 700.7 xanthan (Rhodopol 23P) 4.0NaCI Normapur 177.0 Total 881.7

EXAMPLE 2

In a nitrogen rented round bottom flask, a mixture of methoxypolyethylene glycol (M=750 g/mol) and polyethylene glycol (M=1000 g/mol)respectively 67% and 33% by weight was poured at 50° C. Methoxypolyethylene glycol and polyethylene glycol are bearing respectively 1and 2 OH function per molecule. The necessary quantity of methacrylicanhydride (AM2O) to get a molar ratio of AM2O/OH=1 is added to thereaction medium. Prior use, AM20 was stabilized with 1000 ppmphenothiazine and 1000 ppm topanol.

The quantities and the nature of the used products are reported in thetable 3 below:

supplier purity M (g/mol) m(g) methacrylic anhydride AM2O  94% 154.1625.5 Aldrich PEG 1000 Fluka 100% 1000 33 methoxy PEG 750 Aldrich 100%750 67 phenothiazine Acros  99% 199.3 0.024 topanol A brenntag 78.5-100%178 0.024

The reaction medium was heated up to 80° C. for 10 hrs under stirring ofa magnetic bar (with an expected yield of esterification is 80%).

Flask was then placed under vacuum (30 mbars) and heated to 90° C. Underthese pressure and temperature conditions, produced methacrylic adic wasremoved by vapor stripping. Stripping was considered as complete whenresidual methacrylic acid content is below 2%. The obtained product isdiluted with water to 70%. This material will hereinafter be referred toas “PEO-methacrylate monomers”.

EXAMPLE 3

The capsules from example 1 are formulated with a PEO-methacrylatemonomers from example 2.

Formulations are thickened using hydroxyl-ethyl cellulose (HEC)Cellosize 10-HV from Dow. The solid polymer is hydrated for at least 1hr under stirring in de-ionized water at 0.5% wt prior use.

Other components are gently mixed together in quantities as reported intable 4 below:

formulation #2-1 formulation #2-2 formulation m (g) m (g)PEO-methacrylate monomers 3.75 3.75 HEC at 0.5% 21.25 21.25 Sodiumpersulfate 0.125 0.25 capsules from example 1 0.25 0.25

Half of each formulation is sheared for 10 secs at 16000 RPM using arotor stator blender (Ultra-Turrax 125 basic from IKA). Solution of bothsheared and un-sheared formulations are then let set at 21° C. andsetting times are reported in table 5 below.

formulation #2-1 formulation #2-2 Sheared ultra turrax gelificationafter gelification after 105 mn 65 mn un-sheared gelification aftergelification after 25 hrs 21 hrs

The results gathered in the above table, shows that shear from rotorstator blender can release the polymerization activator and inducegelification of the formulation.

EXAMPLE 4: HIGH TEMPERATURE FORMULATION

In order to ensure a proper temperature stability for thePOE-methacrylate monomers at high temperature, a more thermally stableoxidizer is used and an extra inhibitor is added to the system. Theinhibitor used here is the 4-Hydroxy-2,2,6,6-tetramethylpiperidine1-oxyl (or hydroxyl-TEMPO)

The capsules from example 1 are formulated with a PEO-methacrylatemonomers from example 2.

Formulations are thickened using hydroxyl-ethyl cellulose (HEC)Cellosize 10-HV from Dow. The solid polymer is hydrated for at least 1hr under stirring in de-ionized water at 0.5% wt prior use.

Other components are gently mixed together in quantities as reported intable 6 below.

formulation #3-1 Formulation m (g) PEO-methacrylate monomers 3.75 HEC at0.5% 21.25 tertiobutyl hydroperoxide @ 70% in water 0.10 capsules fromexample 1 0.25 Hydroxy-TEMPO @ 1% in water 0.19

Then half of the formulation is sheared for 10 secs at 16000 RPM using arotor stator blender (Ultra-Turrax T25 basic from IKA). Solution of bothsheared and un-sheared formulations are placed in an oven heated at 80°C. and setting times are reported in table below.

formulation #3 sheared ultra turrax  45 mn un-sheared 210 mn

Considering that in the oven, samples take about 60 minutes to reach 80°C. and are at 65° C. after 45 mn, the above shows that a sheared sampleis activated very quickly once at elevated temperature while anun-sheared sample remains stable for a couple of hours at 80° C. withoutany reaction.

The invention claimed is:
 1. An aqueous gelling system comprising: i)water soluble or dispersable monomers comprising acrylated ormethacrylated polyoxyethylene and/or polyoxypropylene monomers ii) apolymerization initiator dispersed in said monomers i), and iii) anencapsulated polymerization accelerator comprising drops of activatorenclosed in shells of polyurethane dispersed in water, wherein theshells of polyurethane have an average diameter between 300 and 1500 μm,wherein the polymerisation accelerator is an alkylamine,polyalkylenamine, or polyalkylenimine.
 2. The aqueous gelling system ofclaim 1, wherein the encapsulated polymerization accelerator is obtainedin a process comprising the steps of: a) providing a reverse emulsioncontaining, in an oil phase, a water solution or dispersion (W1)containing said polymerisation accelerator, the oil phase including aheat curable mixture of an isocyanate and a hydroxylated polyalkyldieneor polyol, b) pouring the reverse emulsion of step a) in a water phase(W2) to make a water/oil/water multiple emulsion, containing drops ofthe water solution or dispersion comprising the accelerator as theinternal water phase and, then, c) curing the mixture of isocyanate andhydroxylated polyalkyldiene or polyol in the multiple emulsion obtainedin step b) to obtain polyurethane and enclose the drops of the watersolution or dispersion comprising the accelerator in shells of thepolyurethane dispersed in water, wherein the shells of polyurethane havean average diameter between 300 and 1500 μm.
 3. The gelling system ofclaim 2, wherein the hydroxylated polyalkyldiene or polyol is ahydroxylated polybutadiene.
 4. The gelling system as claimed in claim 2,wherein the isocyanate is a trimer form of alpha, omega aliphaticdiisocyanate.
 5. The gelling system of claim 2, wherein thepolymerisation accelerator is a polyethyleneimine (PEI).
 6. The gellingsystem of claim 2, wherein a further polymerization initiator isencapsulated with the polymerization accelerator, wherein thepolymerization initiator is selected from the group consisting of watersoluble persalts and/or peroxides.
 7. The gelling system of claim 2,wherein the water soluble or water dispersable acrylated ormethacrylated polyoxyethylene and/or polyoxypropylene monomers have thegeneral formula:CH₂═CR¹—CO—(O—CH₂—CHR²)n-OR³  (1) wherein: R¹ is a hydrogen atom or amethyl radical, R² is a hydrogen atom or a methyl radical, and R³ is ahydrogen atom, a methyl radical, or a CH₂═CR¹—CO— group, and n is awhole or fractional number from 3 to
 25. 8. The gelling system of claim7, wherein the water soluble or water dispersable acrylated ormethacrylated polyoxyethylene and/or polyoxypropylene monomers is amixture of methacrylate modified polyethylene oxide of the formulae:

wherein n is a number between 15 and 25, limits included, and/or

wherein n is a number between 10 and 20, limits included.
 9. The gellingsystem of claim 7, wherein the water soluble or water dispersablemonomers is a mixture comprising at least two distinct kinds ofmonomers, obtained by reacting a mixture of two compounds (A1) and (A2)having the following formulae:HO—(O—CH₂—CHR²)_(n)—OMe  (A1)HO—(O—CH₂—CHR²)_(n)—OH  (A2) wherein R² and n are as defined in claim 7and Me is a methyl radical, with a (meth)acrylic acid, chloride oranhydride.
 10. The gelling system of claim 9, wherein the molar ratio(A2)/(A1) is from 10:90 to 50:50.
 11. The gelling system of claim 9,wherein the (meth)acrylic anhydride is a (meth)acrylic anhydride offormula (CH₂═CR¹—C(O))₂O wherein R¹ is as defined in claim
 7. 12. Thegelling system of claim 2, wherein the polymerisation accelerator is analkylamine, polyalkylenamine or polyalkylenimine comprising tertiaryamino groups and whose alkyl or alkylen part comprises 2-4 carbon atoms.13. The gelling system of claim 2, wherein the isocyanate is alpha,omega aliphatic diisocyanate.
 14. The gelling system of claim 2, whereinthe shells of polyurethane have an average diameter between 300 and 800μm.
 15. A process for sealing subterranean environments andconsolidation of a soil or sealing of a subterranean structure,comprising underground railway tunnels, sewers, underground car parks,storage ponds, swimming pools, oil wells, mine shafts and dams,comprising the steps of: e1) injecting into said environments soil orstructure an aqueous gelling system of claim 1; and e2) triggering thepolymerisation of the resin by physical means, whereby the encapsulatedpolymerization accelerator is released from the polyurethane capsules.16. The process of claim 15, wherein said physical means is selectedfrom the group consisting of high shear, high pressure, temperature,crushing, shearing, and any combination thereof.